Uncovering new physical phenomena and functional materials is often an exercise in navigating nature's collection of stable, or near-stable, crystal structures. We are interested in exploring this space experimentally to make new phases, examine old ones, and understand how known compounds respond to dopants. We are often guided by theory and computation, while our experimental work utilizes a unique in-situ X-ray diffraction platform that allows us to watch a wide variety of synthesis reactions. I will present recent results from our searches for entirely new compounds, including superconductors, transparent conducting oxides, and low-dimensional magnets. With windows into how materials form, we can critically evaluate computational predictions and explore novel reactions that tilt chemistry in our favor—usually toward the unknown.